A study on template effects using irregular porous isotactic poly(methyl methacrylate) films constructed with syndiotactic rich poly(methacrylic acid) and isotactic poly(methyl methacrylate)

To investigate the stereocomplex formation efficiency with various syndiotactic-poly(methacrylic acids) (st-PMAAs) after the extraction of the syndiotactic-rich PMAA from stereocomplex film, the low syndiotacticity of PMAA (rr=78%) was used to prepare irregular isotactic poly(methyl methacrylate) (it-PMMA)/st-PMAA (rr=78%) stereocomplex thin films on substrates. The resultant irregular porous it-PMMA thin films showed effective incorporation of st-PMAA (rr=78 and 96%), suggesting a structural rearrangement of the it-PMMA main chain. However, the template polymerization in porous it-PMMA thin films with a monomer of methacrylic acid resulted in a stereoregular replica of the st-PMAA, without any rearrangement of the it-PMMA. When irregular stereocomplex formation was employed, these results demonstrated a clear difference between polymer–polymer interactions and polymer–monomer interactions and indicated that a high stereoregularity was necessary to achieve strict control of the stereoregular template polymerization on the porous thin film.